High iodine value oils



July 31, 1945. L.-. o. Bux'roN i HIGH IQDINE .VALUE OILS Filed July 29, 1942 2 sheets-sheet 1 x.. zoCL o@ QQ on ow om o# om QN )414| AI:o zmnzws. lolo.. ...o mz3/2m oom oww

INVNTOR l LORAN 0. BUXTON July-31, 1945.

L` O. BUXTON HIGH IODINE VALUE OILS Filed July 29, 1942 2 Sl'ueets-Sheei'I 2 ATTORNEY Patented July 3l, 1945 HIGH IODINE VALUE OILS Loran Oid Buxton, East Oron. N. J., aaoignor to National Oil Products Company, N. J., a corporation of New Jersey Application July zo, 1942, serum. 452,115

(bl. zoo-42s) 12 Claims.

flaxseed crop, the price of linseed oil is quite fre-- quently relatively high. Because of this and other reasons a number of substitutes for linseed oil have been proposed. Vegetable oils such as soybean oil and similar oils have been suggested. but, although they may be used in admixture with linseed oil, they are not satisfactory as they form soft, gummy films. Fish oils may also be used in conjunction with linseed oil, but even though they usually have a much higher iodine value than the vegetable oils and are fairly rapid driers, they also form soft, tacky films and are therefore no more applicable for use alone than are the. vegetable oils. Much work has been done along the line of developing new and known but not extensively grown plants for producing drying oils and also along the line of chemical processingof the relatively cheap and available oils in order to produce drying oils, but, as yet, no satisfactory, readily available, economical replacement for linseed oil for use in paints or varnishes has been developed.

It is the object of thisinvention to provide a process for producing improved drying oils from iish oils.

Another object of this invention is to provide a low cost drying oil to entirely replace linseed oil in paints andvarnishes.

Still another object of thisinvention is to provide an economical, readily available supply of drying oils for paints and varnishes.

Other objects of the invention will in part be obvious and in part appear hereinafter.

Fish oils are composed essentially of a mixture of triglycerides of various higher fatty acids having varying molecular vweights and varying degrecs of unsaturation. 'Ihe unsaturated triglycerides in ilsh oils have, for the most part, a higher tively saponiiied, leaving a large part of the highly unsaturated fatty acid components of the oil esterliied with glycerol. That part of the fish oil which has been saponied is then separated from the unsaponied fraction the latter of which has an iodine value substantially higher than the original oil and is characterized by having excellent drying and film-forming properties.

In order to bring about the desired selective saponiiication, I have found that it is very important that this reaction proceed slowly under controlled conditions. If the reaction is carried out at a rapid rate, as is usually the case, e. g. in soap manufacture, the saponiiication will not be selective, but instead the more highly unsaturated components of the oil will be saponied as readily .as the saturated components. Consequently, even though the fish oil may be only partially saponiiled if the reaction is carried-out at a fairly rapid rate, the portion of the oil which is not saponied will have practically the same degree of unsaturation as the original oil.

I have found that the ester linkages between the more saturated, the shorter chain and the lower molecular weight fatty acids, and glycerol are not as strong as the ester linkages between the highly unsaturated fatty acids and glycerol: consequently, the former are more readily broken and if the conditions of saponiflcation are properly controlled, such linkages are ruptured whereas the4 linkages between the more highly unsaturated fatty acids and glycerol are not broken. When the saponiiied saturated fatty acids are removed from the partially saponified mixture..

35 the oil which remains is highly unsaturated and from oils of fish origin by' partiallyv saponifying the same in such a manner that the more saturated glyceride components of the oil are selecserves as an excellent drying oil. However, if the conditions of saponiiication are made somewhat more severe the unsaturated fatty acids in some cases split olf from the glycerol as readily as the 'saturated ones, and therefore in suchcases` the degree of unsaturation of the unsaponifled oil,

for all practical purposes. will not have been incre'ased whatsoever.

The invention accordingly comprises the several steps and relation of one or more of such steps with respect to each of the others, and the product possessing the features, properties and the relation of elements, which are exemplified in the following detailed disclosure', and the scope of the invention will -be indicated in the claims.

In suectively and partially saponlrying the ash oil with caustic alkali, the partial saponication y may be carried out without the presence of a solvent medium; however, it is preferred that the selective and partial saponincation be carried out in the presence of a solvent, preferably a hydrocarbon or halogenated hydrocarbon solvent for the sh oil. Suitable solvents in which ish oils may be selectively and'partially saponiiied include, inter alla. ethylene dlchlorido, methylene dichloride, trichloroethylene, heptane, hexane. cyclohexane, methyl cyclohexane, etc., or a mixture of two ormore of these or other solvents for sh oils which will not dissolve any appreciable amount of water or hydrated alkali metal soap.

The oil is preferably diluted with solvent before adding the saponiflcation agent. When the oil is diluted with solvent for carrying out the selective partial saponiication step, the solvent should` comprise from to 99% and preferably 25% to 75% based on the weight of the oil.

'Ihe selective partial saponiiication of the fish oil is preferably edected by slowly stirring a suitable alkaline agent such as sodium carbonate. sodium hydroxide, potassium carbonate or potassium hydroxide, -aqueous potassium hydroxide usually being preferred, into the solvent-diluted oil, care being taken to insure thorough mixing and to avoid too rapid saponiilcation. Alkali is added in quantities suiilcient to saponify to 90% and preferably 40% to 80% of the fish oil being treated. The degree of saponication will be varied considerably depending upon the particular oil treated as well as upon the characteristics desired in the end product.

As a relatively slow rate of saponlfication appears to b e the most favorable for selective'saponiflcation of the more saturated fatty acids, I prefer to carry out the saponiiication at room temperature. In some cases when saponifying at room temperatures (i. e. without supplying heat), it is desirable to employ a saponiflcation catalyst, such as, for example, isopropanol, eth'anol, methanol, etc., to aid in bringing about a reaction between the oil and the alkali. This is particularly true when vsaponifying in the presence of a hydrocarbon or halogenated hydrocarbon solvent. Of course, th'e rate of saponication may be retarded by reducing the amount of saponication catalyst ordinarily u sed, when complete saponiflcation is desired, or by not using any at all, also, by using a less concentrated alkali, etc. If desired, saponiflcation inhibitors may be used to retard the rate of reaction; however, that is seldom necessary when the reaction is carried out at room temperature. `Also, if desired, the rate of saponication may be retarded by carrying the' reaction out 'at a temperature below room temperature.

In separating the unsaponied portion oi' the fish oil from the soaps which h'ave been formed, I prefer to extract the partially saponifled mass with va hydrocarbon or halogenated hydrocarbon solvent, such as one of the solvents suitable for use in diluting the oil prior to the saponiflcation f' step, and preferably the same solvent as was used during the saponification step. Before extracting the selectively partially saponied mass with' solvent, I prefer to adjust the water content thereof to about 22% to about 26% based on the weight of the soap present in the mass, vas usually the separation of the saponied portion from the unsaponifled portion is most elciently accomplished when the moisture content of 'the soap mass is within this range. Of course, the unsaponifled Oil maybe. separated from the soap by other drying properties.

liver oil. mackerel oil, eoleliveroiLspear'sh liver oil, etc. Also. if desired, mixtures of any oftheseorotheriishoilsmaybetreated. The expression fish o is employed herein to connote oils of flshorlgin,i. enshbodyoils andflsh liver oils.

For a'fuller understanding' of th'e nature and objects of the invention, reference should be had to the following examples which are given merely to further illustrate the invention and are not to be construed in a limiting sense, all parts given being by weight.

Example I 200 parts of sardine oil were mixed with 100 parts of ethylene dichloride, 6 parts of 99% isopropanol and 60 parts of 46% aqueous KOH (sumcient to saponify about of the oil). The mixture was then stirred at room temperature for about 20 minutes and the mass left at room temperature over nigh't. .The partially saponifled mass was then mixed with about 600 parts of additional ethylene dichloride, and the mixture warmed to about 40 C. to consulate the soaps. The moisture content of the soap was then increased to about 24 the mixture cooled to about 25 C., and the unsaponiiled fraction extracted with additional batches of fresh'solvent. The extracts were ltered and the solvent removed. The oil thus obtained was light yellow in color.' had an iodine value of 216 and dried rapidly on exposure to air to form a ilrm durable nlm. The original sardine oil had an iodine value of'l86 and on drying formed a soft tacky illm.

scribed in Example I. The resulting oil had an iodine value of 234 and formed a firm durable filmen drying.

' Example III 200 parts of cold pressed sardine oil having an iodine value of 186 were mixed with 100 parts of ethylene dichloride and the mixture agitated for :iv hours at room temperature with 43 parts oi 46% NaOH. The mass was allowed to 'stand at room temperature for about 60 hours. It was then mixed with 600 parts of ethylene dichloride and the water content adjusted to about 24% (based on the weight of the soap). The ethylene dichloride, which contained the major part of the unsaponiiled portion of the oil, was removed, and the remainder of the oil removed from the soap mass by extracting the mass with additional fresh batches of ethylene dichloride. The ex` tracts were filtered and the solvent removed. A light yellow oil resulted having an iodine value vof 208 and characterized by having excellent EzampleIV v parte of 'sardine oil were mixed at room temperature with 30 parte of 46% aqueous KOH (sufficient to saponify about 80% of the bil) in the presence of 15' parts of 99% isopropanol. The mixture was relatively solid in about 6 minutes, and the .temperature of the mixture had increased to 51 C. The partially saponined mass :was allowed to stand overnight, and the unsaponined portion then extracted therefrom with' ethylene dichloride as described in Example I. The oil was light yellow in color and the iodine value was 210 as compared to 183for the original Example V A sample of the same sardine oil as was used in Example 1V was treated in essentially the same manner as in Example IV, the principal difference being that in this case 40% aqueous KOH was used instead of 46%. It was necessary to continue stirring for 11 minutes before the mass became solid enough to hold its shape. At that time the temperature was only 37 C. as compared to 51 C. in Example IV which 'indicates that with the less concentrated caustic, the saponication proceeds at a slower rate. Although the same yield of yoil was obtained in both examples, the iodine value of the oil obtained in thisgcase was 222 as compared to 210 in Example IV. This very clearly illustrates that selective saponiflcation is obtained by varying the saponication conditions, i. e. the milder the conditions, the more-selective the saponitlcation.

Eample VI 100 parts of shark liver oil having an iodine value of 175 were mixed with 50 parts of ethylene dichloride and 1 part of 99% isopropanol. While stirring, suiiicient 46% KOH (22 parts) to vsaponify about 55% of the oil was added and the mixture stirred for hours. 'I'he solid soap was kept at room temperature overnight and then treated further in the usual manner to separate the unsaponifled oil from the partially saponifled mass. The resulting oil was light yellow in colorhad an iodine value of 206 and formed a rm durable film on drying.

Example VII 100 parts of sardine oil having an iodine value of 183 were mixed with 50 parts of ethylene di-v Example VIII 100 parts of herring oil were mixed with 50 of ethylene dichloride, employing 50 parts of ethylene dichloride to every parts of oil. The word catalyst" as used in thev table refers to isopropanol and the percentage given is based on the weight of the oil. All of the saponiilcation reactions were carried out at room temperature. i. e. without supplying any extraneous heat.

Table I Iodine value Saponii Oil nmwm ondltmns l End mal uct Per cent Sardine No. I 79 Solvent 3% catalyst 178 216 Sardine No. 2 75 .do 163 215 Do. 54 dn 183 201 Sardino No. 3 76 do 181 219 Sardina Nn. 4 77 Solvent 3% catalyst. 184 223 medium stirring.

Do... 77 Solvent 3% catalyst 184 230 slow stirring. l1o S0 No solvent 3% cata- 1M 222 y Alyst dilute alkali M" s (40%). Do. $0 o 'solvent 1.5% 184 210 catalyst. Herring. 82 Solvent 3% catalyst 135 169 Cod liver R0 do 149 186 Shark liver No. 1 S0 do 183 234 Sharkliver No.2 74 do |76 216 Do, 25 .d0 176 184 SharkliverNo.3 43 do.. 167 190 Shark liver No. 4 7l No `:oilvcnt 3% cata- 178 212 De 43 do 178 191 'luna llver 37 Solvent 3% catalyst 149 162 Halibut liver 28 do. 137 y151 Menhaden No.1 83 do 171 212 Do. 5l d0 l7l 192 parts of ethylene dichloride. 3 parts of 99% isov propanol and, while stirring, suiiicient 46% aqueous KOH (31 parts) to saponify about 80% of the oil was added. The mass was then treated further much the same as in the above examples. The oil which was obtained had an iodine value of as compared to 135 for the original oil.

Example IX This example was carried out in exactly the same manner as Example VIII, the only diierence being that a sample of cod liver oil having an iodine value of 149 was used in place of herring oil. A very good drying oil having an iodine value of was obtained.

The following table summarizes some of the many experiments which were carried out on word solvent is used in the table to indicate that the reaction was carried out in the presence In the accompanying drawings Figure 1 comprises three curves depicting the increase in iodinevalue of three oils when subjected to varying degrees of partial saponication; Figure 2 comprises four curves illustrating the increase in iodine value when a shark liver oil was subjected to various methods of partial saponiflcation.

In Figure 1, curves l, 2 and 3 represent the increase in iodine value of shark liver oil, sardine oil and menhaden oil, respectively, when subjected to varying degrees of saponication. In each case -100 parts of oil containing 50 parts of ethylene dichloride and 3 parts of isopropanol were reacted to yield 'the indicated degree of saponification. The points plotted on the graph constituting Figure 1 bear the values indicated in the following table:

Oil Sannni- Iodine cation valur` Per cent Shark liver (curve l) (10. 0 178.() Shark liver 28. 5 184. i D0 43.9 192.3 58. 0 203. 3 71 4 212. .i 86. l 223. 0

(10. 0 184. 4 18 6 188. 5 2S (l 191) .'l 11.2 101i S( 5s. 7 201.9 7l. 8 210. R0. 9 217. 5 111'). (l 236. 5

Menhadon (curve 3) (10.() 172. 5 Me iliaden 31. 4 178. 0 52.9 188.5 73. (l 196. 0 83. 4 210. (l 90. 9 231. 0

In Figure 2, curves l, 2, 3 and 4 all represent a shark liver oil subjected to varying degrees of saponiilcation under four separate sets of conditions. 'I'he oil represented by curve l was partially saponiiied by caustic potash without the presence of either solvent or catalyst. The oil represented by curve 2 was partially saponied without the presence of solvent, but in the presence of 0.75% isopropanol. 'I'he oil represented by curve 3 was partially saponiiled without the presence of solvent, but in the presence of 3.0% isopropanol. The oil represented by curve 4 contained 50% ethylene dlchloride and 3.0% isopropanol, based on the weight of the oii, upon partial saponiflcation. The points plotted on the graph constituting Figure 2 bear the values set forth in the following table:

Shark liver oil having original iodine value of The curves shown in Figure 2 clearly reveal the superior results obtained by carrying out the partial selective saponication in the presence of a solvent for the oil along with a small quantity of catalyst. In carrying out the process of the invention on a commercial scale it is advisable to perform preliminary experiments on the particular fish oil to be processed in order to determine the optimum conditions. Fish oils vary considerably in their properties and characteristics and in their reaction or behavior when treated according to the process of this invention. It has been found that different batches of the same' species of iish oil likewise vary. For example,

diiferent batches of shark liver oil were employed in the experiments depicted by curve I of Figure l and curve 4 of Figure 2. The differences in the results obtained are clearly indicated by a comparison of these two curves. Hence, it is important to determine beforehand the behavior of any given fish oil when treated according to the process of the invention.

In practically every case, the drying oil obtained was much lighter in color than the original oil, usually being light yellow. This is another important advantage of my process as light colored oils are much preferred by the industry. Furthermore, the oils produced have lost the major portion of the fishy odor of the original oils, and thus are highly satisfactory in that respect. Also these oils are completely devoid of free fatty acids. The products of my invention are quite fluid and have low cloud and pour points because of the` removal of the more saturated components therefrom.

Drying oils are in many cases bodied before saturated character, my drying oils are much more adaptable to being bodied than are many of the natural drying oils. Furthermore. because of their highly unsaturated character, my drying oils may be readily sulfonated yielding products of high SO: content.

The partial saponication of fish oils in addition to selectively saponifying the more saturated components thereof also destroys the major portion of any natural antioxidants that may be present in the oil. Consequently, the rate of drying of the oil is still further increased. Thus, by eliminating the majority of the more saturated components of the oill and the major portion of the natural antioxidants therein, an oil having a very high iodine value and rapid drying qualities is obtained. If desired, the iodine value of the unsaponilied portion of the partially saponined oil which is obtained may be further stepped up by solvent fractionation or other conventional means.

The soaps which are formed as by-products of the process of my invention may be utilized for various purposes, e. g.A they may be split by acid hydrolysis and the fatty acids recovered and used as such or for other purposes for which they are adapted. Since the major part of the fatty acids in those soaps are much more highly saturated than is usually the case with fish oil' soaps, the soaps which are produced as by-products of my invention are in many cases more useful than the ordinary iish oil soaps. The high iodine value fraction produced in accordance with this invention may be hydrolyzed to produce highly unsaturated fatty acids of high molecular weight. Thus, it may be seen that this invention affords a means of recovering from fish oils the higher molecular weight fatty acids, i. e. acids containing 20 or more carbon atoms.

Since certain changes in carrying out the above process and certain modiications in the composition which embody the invention may be made without departing from its scope, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

Having described my invention, what I claim as new and desire to secure by Letters Patent is:

1. A process of producing high iodine value oils from fish oils which comprises selectively saponifying 30% to 90% of a fish oil by means of an alkali to split saturated glycerides and separating the unsaponified fraction from the resulting soap mass.

2. A process of producing high iodine value oils from sh oils which comprises admixing a sh oil with a lesser quantity of a water-immiscible organic solvent therefor, saponifying 30% to 90% of the fish oil by means of an alkali and separatbeing used, either by heating at atmospheric presing the unsaponied fraction from the saponied mass.

3. A process of producing high iodine value oils from fish oils which comprises admixing a sh oil with a lesser quantity of a hydrocarbon solvent therefor, saponifying 30% to 90% of the fish oil by means of an alkali and separating the unsaponied fraction from the saponiiied mass.

4. A process of producing high iodine value oils from sh oils which comprises admixing a fish oil with a lesser quantity of a halogenated hydrocarbon solvent therefor, saponifying 30% to 90% of the fish oil by means of an alkali and separating the unsaponlfied fraction from the saponied mass.

5. A process of producing high iodine value oils from sh oils which comprises admixing a fish oil with a lesser quantity of ethylene dichloride, saponifying 40% to 80% of the ilsh oil by means of an alkali and separating the unsaponided fraction from the saponiiied mass.

6. A process of producing high iodine value oils from fish oils which comprises admixing a sh oil with a lesser quantity of a therefor, saponifying 30% to 90% of the iish oil by means of an alkali in the presence of a saponifying catalyst and separating the unsaponiiied fraction from the saponied mass.

'7. A process of producing high iodine value oils from fish oils which comprises admixing a iish oil with a lesser quantity of ethylene dichloride, saponifying 40% to 80% of the fish oil by means of an alkaliin the presence of a small quantity of isopropanol and separting the unsaponied iraction from the saponied mass. u

8.v A process of producing high iodine value oils from fish oils which comprises admixing in the presence of an alcoholic saponiiication catalyst a sh oil having a lesser quantity of a Water-irnniiscible organic solvent dissolved therein with a quantity of alkali suiicient to saponify 30% to 90% of the iish oil, stirring the mass to form a super-solvented emulsion, breaking the emulsion by means of heat to occulate the soap, adding a further quanity of Water-immiscible organic solvent to cause complete separation of the fiocculated soap particles and separating the solvent solution of the unsaponiiied high iodine value oil from the soap particles.

9. A process of producing high iodine value oils from sh oils which comprises admixing in the presence of an alcoholic saponication catalyst a fish oil having a lesser quantity of ethylene dichloride dissolved therein with a quantity of a1- kali suiilcient to saponify 30% to 90% of the fish oil, stirring the mass to form a super-solvented emulsion, breaking the emulsion by means of heat to flocculate the soap, adding a further quantity of ethylene dichloride to cause complete separahydrocarbon solvent tion of the iiocculated soap particles and separating the solvent solution of the unsaponied high iodine value oil from the soap particles.

10. A l`process of producing high iodine value oils from iish oils which comprises admixing in the presence of isopropanol a fish oil having a lesser quantity of ethylene dichloride dissolved .therein with a quantityof alkali sufiicient to saponify 40% to 80% of the ish oil, stirring the mass to form a super-solvented emulsion, breaking the emulsion by means of heat to occulate the soap, adding a further quantity of ethylene dichloride to cause complete separation of the flocculated soap particles and separating the solvent solution of the unsaponiiied high iodine value oil from the soap particles.

11. A process of producing high iodine value oils from iish oils which comprises admixing in the presence of isopropanol a sardine oil'having a lesser quantity of ethylene dichloride dissolved therein with a quantity of alkali sufficient to saponiiy 40% to 80% of the said oil, stirring the mass to form a super-solvented emulsion, breaking the emulsion by means of heat to flocculate the soap, adding a further quantity of ethylene dichloride to cause complete separation of the l iiocculated soap particles and separating the solthe vent solution of the unsaponied high iodine value oil from the soap particles.

12. A process of producing high iodine value oils from ilsh oils which comprises admixing in the presence of isopropanol menhaden oil having a lesser quantity of ethylene dichloride dissolved therein with a quantity of alkali sufcient to saponify 40% to 80% of the said oil, stirring the mass to form a super-solvented emulsion, breaking the emulsion' by means of heat to .fiocculate soap, adding a further quantity of ethylene dichloride to cause complete separation of the fiocculated soap particles and separating the solvent solution of the unsaponied high iodine value oil from the soap particles. 

